Time-of-flight spectra of the nascent H atoms, and laser induced fluorescence excitation spectra of the nascent NH 2 radicals, are leading to a very complete knowledge of the energy disposal following photodissociation of NH 3 through its A 1 A 2 excited state. Both the dissociation rates and the product distributions are sensitive to the values of the vibrational and rotational quantum numbers of the quasi-bound levels of the parent molecule. The most populated fragment states involve the a-axis rotational, and bending vibrational, motions of the NH2 with modest excitation of further rotational degrees of freedom at low internal energy. For most NH 2 internal states the accompanying H atoms recoil close to the initial plane of NH 3 excitation, but for a specific subset of product states the H atoms recoil perpendicular to this plane. These measurements and their interpretation give a detailed insight into the intramolecular motion of the dissociating NH3 molecule, which is dynamically controlled but yet involves most of the internal degrees of freedom.
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